Professional Documents
Culture Documents
Abstract
Emerging technological knowledge is leading research into new ventures. One such is the conversion of natural oils to
polymers to augment the use of petroleum products as the source of polymeric raw materials. Natural oils, such as vegetable
oils, now mainly used in the food industry, offer alternatives, and recent research has studied new routes of synthesis of
polymers from natural oils. This review paper discusses the synthesis and characterization of new polymers from different
natural oils such as soybean, corn, tung, linseed, castor, and sh oil. The effects of different levels of unsaturation in the
natural oils and various types of catalysts and comonomers on the properties of copolymers are considered.
r 2006 Elsevier Ltd. All rights reserved.
Keywords: Natural oils; Dynamic mechanical analysis; Cross-linking; Polymerization; Drying oil; Glass transition temperature
Contents
1.
2.
3.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 984
Polymers from natural oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 985
2.1. Soybean oil polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 985
2.1.1. Unmodied soybean oil polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 985
2.1.2. Modied soybean oil polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 992
2.2. Fish oil polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 994
2.3. Corn oil polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 995
2.4. Tung oil polymers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 996
2.5. Linseed oil polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 998
2.5.1. Natural linseed oil polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 998
2.5.2. Epoxidized linseed oil polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1002
2.6. Castor oil polymers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1003
2.7. Polymers from other oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1004
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1005
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1006
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1006
ARTICLE IN PRESS
V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 9831008
984
1. Introduction
In recent years natural oils have attracted
renewed attention as raw materials for the preparation of resins and polymeric materials, to replace or
augment the traditional petro-chemical based polymers and resins. Natural oils such as linseed and
tung oil have long found various uses in the paint
and varnishes industries. These oils have traditionally been used in organic coatings either as resins or
as a raw material for the preparation of resins.
Soybean oil, safower oil, sunower oil and canola
oil have also been used in polymerizations.
Natural oils are tri-glyceride esters of fatty acids,
the general structure of which is shown in Fig. 1.
Triglycerides comprise three fatty acids joined by a
glycerol center [1]. Most of the common oil contains
fatty acids that vary from 14 to 22 carbons in
length, with 13 double bonds. The fatty acid
distribution of several common oils is shown in
Table 1 [1]. In addition, there are some oils comprise
fatty acids with other types of functionalities (e.g.,
O
O
O
O
Fig. 1. The triglyceride chain containing three fatty acid chains joined by a glycerol center. Reprinted with permission from Polymer 2001;
42: 1569 r Elsevier Science Ltd., [10].
Table 1
Main fatty acid contents in different oils
Fatty acid
[#C: #DB] Canola oil Corn oil Cottonseed oil Linseed oil Olive oil Soybean oil Tung oil Fish oily
Palmitic
Stearic
Oleic
Linoleic
Linolenic
a-elaeostearic acid
Average #DB/triglyceride.
16:0
18:0
18:1
18:2
18:3
4.1
1.8
60.9
21.0
8.8
3.9
10.9
2.0
25.4
59.6
1.2
4.5
21.6
2.6
18.6
54.4
0.7
3.9
5.5
3.5
19.1
15.3
56.6
6.6
13.7
2.5
71.1
10.0
0.6
2.8
11.0
4.0
23.4
53.3
7.8
4.6
4
8
4
84
7.5
18.20
1.10
0.99
3.6
Reproduced with the permission from J Appl Polym Sci 2001; 82: 703 r John Wiley and Sons, Inc. [1].
#C stands for number of carbon atoms in chain and #DB stands for the number of double bonds in that chain.
y
Fish oils tend to contain a high double bond content; for example, the composition of a Norway sh oil examined in one study
contained a fatty acid (ethyl ester) composition with 8.90% having no double bonds, 6.03% having four double bonds, 37.25% having
EPA or DPA and 24.72% (DHA) having six double bonds [29].
ARTICLE IN PRESS
V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 9831008
O
CH
CH2
CH
CH2
CH2
HC
CH2
O
CH
CH
985
CH2
CH
CH2
Fig. 2. The cross-linking process of bacterial polyester obtained from soybean oily fatty acids. Reprinted with the permission from Polym
Bull 2001; 46: 393 r Springer-Verlag, Inc. [24].
CH
CH
CH
CH
CO2
CH
CO2
CH
CO2
O
H2C
O
C
CH2
CH
HC
m
CH
CH
O
O
C
CH
CH
O
CH2
CH
n
CH
CH2
CH
Scheme 1. The proposed process of cross-linking of natural oil with styrene and divinylbenzene in presence of modied initiator.
Reprinted with the permission from J Appl Polym Sci 2003; 90: 1832 r Wiley Periodicals, Inc. [30].
ARTICLE IN PRESS
986
Scheme 2. The modication of acrylated epoxidized soybean oil (AESO) shown using cyclohexane dicarboxylic anhydride or maleic
anhydride. These AESOs were cured with styrene or other comonomers. Reprinted with the permission from J Appl Polym Sci 2001; 82:
707 r John Wiley and Sons, Inc. [1].
ARTICLE IN PRESS
V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 9831008
987
Table 2
The composition of the soybean oils used for the preparation of copolymers
Soybean oil
Fatty acidsb
CQQC
Type
No.a
C16:0
C18:0
C18:1
C18:2
C18:3
Non-conjugated
Non-conjugated
Conjugated
4.5
5.1
5.1
10.5
5.0
5.0
3.2
3.0
3.0
22.3
20.0
20.0
54.4
64.0
64.0
8.3
9.0
9.0
Reproduced with the permission from J Polym Sci: Part B: Polym Phys 2000; 38: 2722 r John Wiley and Sons, Inc. [12].
a
The average number of carbon-carbon double bonds was calculated by 1H NMR spectral analysis.
b
For example, C18:2 represent the fatty acid (ester) that possesses 18 carbons and 2 CQQC bonds.
Fig. 3. The 1H NMR spectra of different soybean oils. (a) regular soybean oil, (b) low saturated soybean oil and (c) conjugated low
saturated soybean oil. Reprinted with permission from J Appl Polym Sci 2001; 80: 660 r John Wiley and Sons, Inc. [11].
ARTICLE IN PRESS
V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 9831008
988
Table 3
The results from copolymerization of different soybean oils using different modied initiator system with styrene and divinylbenzene,
norbornadiene or dicyclopentadiene
Original composition (wt%)
Triglyceride oil
Comonomers
Initiators
45%
45%
45%
45%
45%
45%
45%
45%
45%
45%
32%ST+15%DVB
32%ST+15%DVB
32%ST+15%DVB
32%ST+15%DVB
32%ST+15%DVB
32%ST+15%DVB
32%ST+15%DVB
32%ST+15%DVB
32%ST+15%NBD
32%ST+15%DCP
5%SG-I+3%BFE
5%SG-II+3%BFE
5%SG-III+3%BFE
5%NFO+3%BFE
5%NFO+3%BFE
5%NFO+3%BFE
5%NFO+3%BFE
5%NFO+3%BFE
5%NFO+3%BFE
5%NFO+3%BFE
LSS
LSS
LSS
LSS
SOY
LSS
CLS
CLS
CLS
CLS
3.0 102
3.0 102
3.0 102
3.0 102
2.4 102
3.0 102
6.6 102
6.6 102
3.5 103
2.1 105
83
82
83
84
80
84
92
92
89
80
Reproduced with the permission from J Appl Polym Sci 2001; 80: 662 r John Wiley and Sons, Inc. [11].
Table 4
The DMA, TGA, and Soxhlet extraction results for the samples prepared by copolymerization of soybean oil and divinylbenzene in the
presence of modied initiator
Polymer samplea
SOY60-DVB35-BFE5
SOY50-DVB35-(NFO10-BFE5)
SOY55-DVB30-(NFO10-BFE5)
SOY60-DVB25-(NFO10-BFE5)
LSS60-DVB35-BFE5
LSS50-DVB35-(NFO10-BFE5)
LSS55-DVB30-(NFO10-BFE5)
LSS60-DVB25-(NFO10-BFE5)
CLS50-DVB35-(NFO10-BFE5)
CLS55-DVB30-(NFO10-BFE5)
CLS60-DVB25-(NFO10-BFE5)
Eroom(Pa) 108
4.0
5.0
2.5
1.7
6.0
7.0
3.8
1.9
12
10
7.8
ne(mol/m3) 103
7.60
11.6
6.51
4.18
10.4
13.0
8.35
4.18
18.9
11.4
7.21
Tg(1C)
Structure (wt%)
TGA (1C)
b
a1
a2
Cross-linked
Free oil
Inc. oil
T10
T50
27
70
15
20
37
70
30
17
90
80
68
10
5
0
0
8
0
-
69
77
75
73
82
84
80
77
88
86
86
31
23
25
27
18
16
20
23
22
14
14
29
37
40
43
42
44
45
47
48
51
56
415
425
380
360
423
425
405
395
440
436
433
490
491
475
470
485
486
486
485
485
486
483
Reproduced with the permission from Polymer 2001; 42: 1573 r Elsevier Science Ltd., [10].
Eroom Youngs modulus at room temperature.
ne Cross-linking density.
a
Here SOY represents regular soybean oil, LSSLow saturated soybean oil, CLSconjugated low saturated soybean Oil, DVB
divinylbenzene, NFONorway Pronova sh oil ethyl ester and BFE boron triuoride diethyl etherate. The numerals, such as SOY60
represents 60 wt% of soybean oil.
b
Wt% of oil incorporated into the cross-linked network.
ARTICLE IN PRESS
V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 9831008
989
Table 5
The tensile test results for various soybean oils
Polymer sample
Tg (1C)
ne (mol/m3) 102
E (mpa)
sb (mpa)
eb (%)
Toughness (mpa)
SOY45st32-DVB15-(NFO5-BFE3)
LSS45st32-DVB15-(NFO5-BFE3)
CLS45st32-DVB15-(NFO5-BFE3)
68
61
76
1.8
5.3
22
71
90
225
4.1
6.0
11.5
57.1
64.1
40.5
1.67
2.86
4.00
Reproduced with the permission from J Polym Sci: Part B: Polym Phys 2000; 39: 62 r John Wiley and Sons, Inc. [13].
Tg Glass transition temperature.
ne Cross-linking density.
E Youngs modulus.
sb Ultimate tensile strength.
eb Elongation at break.
1.5
1. E+10
SOY45-ST32-DVB15-(NFO5-BFE3)
LLS45-ST32-DVB15-(NFO5-BFE3)
CLS45-ST32-DVB15-(NFO5-BFE3)
1. E+08
Tan
1. E+09
1. E+07
0.5
1. E+06
SOY45-ST32-DVB15-(NFO5-BFE3)
LSS45-ST32-DVB15-(NFO5-BFE3)
CLS45-ST32-DVB15-(NFO5-BFE3)
1. E+05
-35
-15
25
45
65
85
105
125
Temperature (C)
0
-35
-15
25
45
65
Temperature
85
105
125
ARTICLE IN PRESS
V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 9831008
990
SOY45-ST32-DVB15-(NFO5-BFE3)
LLS45-ST32-DVB15-(NFO5-BFE3)
CLS45-ST32-DVB15-(NFO5-BFE3)
Stress (MPa)
12
0
0
20
40
Strain (%)
60
80
Fig. 7. The SEM micrograph of sample CLS35ST39-DVB18(NFO5-BFE3) highlighting the mechanically fractured surface of
the sample and the mist region of the mechanically fractured
surface. Reprinted with permission from J Polym Sci: Part B:
Polym Phys 2000; 39: 75 r John Wiley and Sons, Inc. [13].
ARTICLE IN PRESS
V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 9831008
991
Table 6
Results for the damping properties of the copolymers prepared from different soybean oils
Polymer sample
Tg(1C)
ne(mol/m3)
(tan d)max
(tan d)rt
TA (K)
Half-width (1C)
SOY35st39-DVB18-(NFO5-BFE3)
SOY45st32-DVB15-(NFO5-BFE3)
SOY55st25-DVB12-(NFO5-BFE3)
LSS35st39-DVB18-(NFO5-BFE3)
LSS45st32-DVB15-(NFO5-BFE3)
LSS55st25-DVB12-(NFO5-BFE3)
CLS35st39-DVB18-(NFO5-BFE3)
CLS45st32-DVB15-(NFO5-BFE3)
CLS55st25-DVB12-(NFO5-BFE3)
79
68
30
80
61
32
82
76
38
4.7 102
1.8 102
1.0 102
7.3 102
5.3 102
3.9 102
3.4 103
2.2 103
6.5 102
0.88
0.85
0.84
0.86
0.89
1.00
0.94
0.79
1.08
0.12
0.32
0.83
0.11
0.37
0.96
0.07
0.18
0.80
52115 (63)
23113 (90)
265 (67)
23113 (90)
1997 (78)
683 (89)
58116 (58)
48120 (72)
1077 (67)
37.5
48.4
36.3
48.4
46.2
50.1
41.8
43.1
52.9
47
61
51
51
52
57
42
53
44
Reproduced with permission from Polymers for Advanced Technologies 2002; 13: 439,441 r John Wiley and Sons, Ltd., [14].
Tg Glass transition temperature.
ne Cross-linking density.
(tan d)max Loss tangent maxima.
(tan d)rt Loss tangent at room temperature.
TA tan d area.
120
100
Tg (C)
80
60
40
20
SOY45-(ST+DVB) 47-(NFO5-BFE3)
LSS45-(ST+DVB) 47-(NFO5-BFE3)
CLS45-(ST+DVB) 47-(NFO5-BFE3)
0
10
100
1000
e
10000
100000
(mol/ m3)
ARTICLE IN PRESS
992
Table 7
Shape memory properties of soybean oil polymers
Polymer sample
SOY45ST32-DVB15-(NFO5-BFE3)
LSS45ST32-DVB15-(NFO5-BFE3)
CLS45ST32-DVB15-(NFO5-BFE3)
SOY45ST32-(DVB5-NBD5-DCP5)-(NFO5-BFE3)
(SOY22.5-LSS22.5)-ST32-(DVB5-NBD5-DCP5)-(NFO5-BFE3)
(SOY15-LSS15-CLS15)-ST32-(DVB5-NBD5-DCP5)-(NFO5-BFE3)
SOY45ST20-(DVB9-NBD9-DCP9)-(NFO5-BFE3)
(SOY22.5-LSS22.5)-ST20-(DVB9-NBD9-DCP9)-(NFO5-BFE3)
(SOY15-LSS15-CLS15)-ST20-(DVB9-NBD9-DCP9)-(NFO5-BFE3)
Tg (1C)
68
61
76
42
43
44
68
70
74
ne (mol/m3)
1.8 102
5.3 102
2.2 103
9.8 10
1.3 102
2.7 102
3.1 102
3.7 102
5.2 102
FD
100
86
77
100
100
100
100
100
100
80
96
98
63
74
75
97
98
99
100
100
100
100
100
100
100
100
100
Reproduced with permission from Journal of Applied Polymer Science 2002; 84: 1539 r John Wiley and Sons, Ltd., [15].
Tg Glass transition temperature.
ne Cross-linking density.
D Deformability of the material at temperature higher than Tg.
FD Degree to which the deformation is xed at ambient temperature.
R Final shape recovery.
Fig. 9. The 1H NMR spectra of acrylated epoxidized soybean oil (AESO). Reprinted with the permission from J Appl Polym Sci 2001;
82: 710 r John Wiley and Sons, Inc. [1].
group. Various chemical pathways for functionalization of these triglycerides have been studied.
LaScala and Wool et al. [1] analyzed optimization
of the effect of chemical functionalization on the
mechanical properties and thermal stability of some
resins. The viscoelastic properties of resin samples
made of AESO and cured at room temperature with
varying amounts of styrene were studied. The 1H
NMR spectra of AESO are shown in Fig. 9. Some
triglyceride-based monomers prepared from acrylic
acid are shown in Fig. 10. It was found that both E0
and Tg increased with increasing styrene content in
the copolymers. The styrene content at 33.3 wt%, or
a 2:1 AESO to styrene ratio, was considered optimal
ARTICLE IN PRESS
V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 9831008
993
O
O
OH
O
O
OH
OH
OH
O
O
O
O
OH
O
O
O
O
O
O
O
OH
HO
O
O
OH
O
HO
O
OH
O
O
OH
OH
HO
O
O
O
HO
O
Fig. 10. Different triglyceride-based acrylic monomers. Reprinted with the permission from J Appl Polym Sci 2001; 82: 706 r John Wiley
and Sons, Inc. [1].
ARTICLE IN PRESS
V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 9831008
994
100% AESO
80% AESO
60% AESO
50% AESO
Tan
0.6
0.5
0.4
0.3
0.2
0.1
-150
-100
-50
50
100
150
200
Temperature (C)
Saturated units:
x = 2 for hexanoate.
x = 4 for octanoate.
x = 6 for decanoate.
Unsaturated units:
y = 0 for -ene.
y = 1 for -diene.
y = 2 for -triene.
z = 1-3.
CH3
CH
HC
CH2
HC
CH3
CH2
O
CH
CH
O
CH2
x
CH2
CH
O
CH2
PHA-Soybean
Fig. 12. The structure of poly(hydroxy alkanoate) (PHA) containing unsaturated side chains of fatty acids, PHAsoybean. Reprinted with
the permission from Polymer Bulletin 2001; 46: 391 r Springer-Verlag, Inc. [24].
ARTICLE IN PRESS
V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 9831008
1.0
1e+10
Polystyrene
0.8
1e+9
0.6
Tan
Epoxy
CFO-DVB-38
1e+8
Polyethylene
0.4
Polystyrene
Polyethylene
1e+7
0.2
Epoxy
CFO-DVB-38
1e+6
50
100
150
200
0.0
250
Temperature (C)
Fig. 13. The comparison of the storage modulus (E0 ) and loss
factor (tan d) for conjugated sh oil (CFO-DVB-38) and some
commercially available polymers. Reprinted with the permission
from Polymer 2000; 41: 7935 r Elsevier Science Ltd., [25].
995
ARTICLE IN PRESS
V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 9831008
996
Fig. 14. The SEM micrograph of the mechanically fractured surfaces of samples NFO49ST33-DVB15-BFE3, CFO49ST33-DVB15-BFE3
and TFO49ST33-DVB15-BFE3. Reprinted with the permission from Polymer 2001; 42: 10144 r Elsevier Science Ltd. [29].
1.0E+10
COR35-ST39-DVB18-(NFO5-BFE3)
COR45-ST32-DVB15-(NFO5-BFE3)
COR55-ST25-DVB12-(NFO5-BFE3)
1.0E+9
1.0E+8
1.0E+7
1.0E+6
1.0E+5
0.6
0.4
0.2
0
-50
50
100
150
200
Temperature (C)
ARTICLE IN PRESS
Wt % of cross-linked polymer
100
100
35C
40C
80
80
60
60
40
40
20
20
COR-ST-DVB
CCOR-ST-DVB
0
0
(a)
997
100
200
300
Cure Time (min)
400
0
(b)
20
40
60
80
Corn Oil Contents (%)
100
Fig. 16. (a) show the dependence of the weight percent of the cross-linked polymer obtained from COR45ST32-DVB15-(NFO5-BFE3) on
cure time at 35 and 45 1C and; (b) the weight percentage of cross-linked polymers prepared from conjugated and simple corn oil versus
corn oil contents. Reprinted with the permission from J Appl Polym Sci 2003; 90: 1833 r Wiley Periodicals, Inc. [30].
100
Recovery (%)
80
60
Fig. 18. The structure of a-elaeostearic acid. Reprinted with the
permission from Biomacromolecules 2003; 4: 1018 r American
Chemical Society [34].
40
20
COR45-ST32-DVB15-(NFO5-BFE3)
CCOR45-ST32-DVB15-(NFO5-BFE3)
0
20
40
60
Temperature (C)
80
100
Fig. 17. The study of the shape-recovery results for the polymer
from conjugated and regular corn oil for sample with composition OIL45ST32-DVB15-(NFO5-BFE3) at different temperatures. Reprinted with the permission from J Appl Polym Sci 2003;
90: 1836 r Wiley Periodicals, Inc. [30].
ARTICLE IN PRESS
998
Fig. 19. The 1H NMR spectra of (a) tung oil (TUN), (b) styrene
(ST), (c) divinylbenzene (DVB) and (d) the extracted soluble
substances from the sample TUN50ST20-DVB30 bulk polymer.
Reprinted with the permission from Biomacromolecules 2003; 4:
1021 r American Chemical Society [34].
ARTICLE IN PRESS
V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 9831008
999
Scheme 3. The autoxidation process for the curing of linseed oil showing initiation, propagation and termination steps of the reaction.
Reprinted with the permission from Prog Org Coat 1998; 33: 220 r Elsevier Science S. A. [42].
ARTICLE IN PRESS
V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 9831008
1000
through reaction of hydroxyl-containing oil specimens with vinyl monomer and then this macromer
was homopolymerized or copolymerized with styrene [47]. Semidrying and non-conjugated oils were
mixed with conjugated drying oils to produce
homogeneous styrenated products [48]. When classical and macromer methods were compared, it was
found that macromer technique resulted in homogeneous products in high yield.
The effect of cobalt-2-ethylhexanoate drier on the
oxidative polymerization of linseed oil was investigated [49]. It was found that the cobalt catalysts
accelerated all of the oxidation reactions involved in
the process, and improved the formation of a solid
lm at the surface, but a viscous oil remained under
this surface lm. The addition of cobalt drier only
inuenced the kinetics, but did not alter the reaction
products.
Exotherm
20
40
60
Time (min)
80
100
OH
OH
O
O
O
O
Linseed Oil
OH
Castor Oil
Interesterification
OH
O
O
OH
OH
OH
O
O
OH
O
O
O
OH
OH
O
O
OH
OH
OH
OH
O
O
OH
Styrene
O
O
O
Macromer
OH
O
O
CH
CH CH2
CH
n
Styrenated Oil
Scheme 4. Styrenation of the linseed oil and castor oil through interesterication of oils which react with acrylic acid and nally with
styrene to form styrenated oil. Reprinted with the permission from Macromol Mater Eng 2000; 283: 17 r WileyVCH Verlag GmbH [44].
ARTICLE IN PRESS
V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 9831008
1001
O
O
OH
OH
OH
OH
O
OH
O
O
OH
Glycerol
Triglyceride Oil
OH
O
OH
O
OH
O
CH3
-CH3OH
H2C
C O
O CH3
O
O
CH3
O
C
CH2
O
O
O
O
O
C
CH3
C CH2
C
O
O O
Benzoyl peroxide
O H3C
C
C
CH2
CH2
CH3
H2C
HC
O
O
CH2
CH3
CH2
CH2 CH
O
O
O
O
O
CH2
H3C
HC
H2C
O
O
O
O
CH3
O
C
Benzoyl peroxide
H3C
C CH2
O
O O
O
O
O
C CH2
CH2 CH
CH2 CH
H3C
Styrenated Oil
Scheme 5. The process of preparation of the partial glyceride and then the styrenation of the partial glyceride through free radical
mechanism in presence of benzoylperoxide. Reprinted with the permission from J Appl Polym Sci 2003; 88: 237475 r Wiley Periodicals,
Inc. [45].
ARTICLE IN PRESS
V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 9831008
1002
0.4
0.35
0.3
0.25
100
Tan
E (MPa)
1000
0.2
0.15
0.1
10
0.05
1
-140
0
- 80
20
40
Temperature (C)
100
160
O
O
O
+
7
O
NLO--25
0.76-0. 90 MPa
NLO--50
250 C
NLO--100
H2O2 /Tungstate
60 C
O
O
O
O
7
NLO--25
[a]
7
O
NLO--50
O
O
7
7
O
O
NLO--100
7
ENLO--25
[b]
ENLO--50
ENLO--100
Scheme 6. The reaction process of the preparation of the norbornane linseed oil (NLO) and epoxynorbornane linseed oil (ENLO).
Reprinted with the permission from J Polym Sci: Part A: Polym Chem 2003; 41: 3444 r Wiley Periodicals, Inc. [50].
ARTICLE IN PRESS
V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 9831008
1003
Fig. 22. The 1H NMR spectra of (a) linseed oil, (b) norbornane linseed oil and (c) epoxynorbornane linseed oil. Reprinted with the
permission from J Polym Sci: Part A: Polym Chem 2003; 41: 3446 r Wiley Periodicals, Inc. [50].
ARTICLE IN PRESS
V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 9831008
1004
70
60
50
40
30
20
10
Neat ENLO-100
1% DEGDVE in ENLO-100
5% DEGDVE in ENLO-100
20% DEGDVE in ENLO-100
0
-10
0
50
100
150
200
Irradiation Time (sec.)
250
300
70
60
50
40
30
20
Neat ENLO-100
2 % DEGDEE in ENLO-100
6 % DEGDEE in ENLO-100
20 % DEGDEE in ENLO-100
10
0
-10
0
50
100
150
200
Irradiation Time (sec.)
250
300
ARTICLE IN PRESS
V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 9831008
1005
Photolysis of Photoinitiator
[b]
[Ar 2 I + X + ] +
Ar 2 I + X +
[a]
ArI*
ArI
X*
ArI*
X*
+ R + H*X*
Initiation
[c]
H+ +
[d]
H+ +
H O+
H
O
O+
Propagation
[e]
H O+
H O
O+
O
[f]
[h]
O O
O H
O
Homopolymer (I)
[g]
O
+ H O
H
O+
O H
[i]
O+
[j]
O H
O
O
Homopolymer (II)
O
[L]
Scheme 7. The mechanism for the photoinitiated cationic polymerization of the epoxynorbornane linseed oil (ENLO). Reprinted with the
permission from J Polym Sci: Part A: Polym Chem 2003; 41: 3454 r Wiley Periodicals, Inc. [50].
ARTICLE IN PRESS
V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 9831008
1006
Acknowledgements
100
80
C87LIN30-ST28-DVB42 (S1)
C87LIN40-ST24-DVB36 (S2)
C87LIN50-ST20-DVB30 (S3)
60
C87LIN60-ST12-DVB28 (S4)
C87LIN70-ST08-DVB22 (S5)
40
References
20
0
0
100
200
300
400
500
600
700
Temperature (C)
[1] Khot SN, Lascala JJ, Can E, Morye SS, Williams GI,
Palmese GR, et al. Development and application of
triglyceride-based polymers and composites. J Appl Polym
Sci 2001;82(3):70323.
[2] Gunstone F. Fatty acid & lipid chemistry. New York:
Blackie Academic & Professional; 1996.
[3] Cunningham A, Yapp A. Liquid polyol compositions. US
Patent, 3,827,993, 1974.
[4] Bussell GW. Maleinized fatty acid esters of 9-oxatetracyclo4.4.1.2,5O1,6O8,10 undecan-4-ol. US Patent, 3,855,163,
1974.
[5] Hodakowski LE, Osborn CL, Harris EB. Polymerizable
epoxide-modied compositions. US Patent, 4,119,640, 1975.
[6] Trecker DJ, Borden GW, Smith OW. Method for curing
acrylated epoxidized soybean oil amine compositions. US
Patent, 3,979,270, 1976.
[7] Trecker DJ, Borden GW, Smith OW. Acrylated epoxidized
soybean oil amine compositions and method. US Patent,
3,931,075, 1976.
[8] Salunkhe DK, Chavan JK, Adsule RN, Kadam SS. World
oilseeds: chemistry, technology and utilization. New York:
Van Nostrand Reinhold; 1992.
[9] Force CG, Starr FS. Vegetable oil adducts as emollients in
skin and hair care products. US Patent, 4,740,367, 1988.
[10] Li F, Hanson MV, Larock RC. Soybean oildivinylbenzene
thermosetting polymers: synthesis, structure, properties and
their relationships. Polymer 2001;42:156779.
[11] Li F, Larock RC. New soybean oilstyrenedivinylbenzene thermosetting copolymers I: synthesis and characterization. J Appl Polym Sci 2001;80:65870.
[12] Li F, Larock RC. New soybean oilstyrenedivinylbenzene
thermosetting copolymers II: dynamic mechanical properties. J Polym Sci B Polym Phys 2000;38:272138.
[13] Li F, Larock RC. New soybean oilstyrenedivinylbenzene
thermosetting copolymers III: tensile stressstrain behavior.
J Polym Sci B Polym Phys 2001;39:6077.
[14] Li F, Larock RC. New soybean oilstyrenedivinylbenzene
thermosetting copolymers IV: good damping properties.
Polym Adv Technol 2002;13:43649.
[15] Li F, Larock RC. New soybean oilstyrenedivinylbenzene thermosetting copolymers V: shape-memory effect.
J Appl Polym Sci 2002;84:153343.
[16] Li F, Hou J, Zhu W, Zhang X, Xu M, Luo X, et al.
Crystallinity and morphology of segmented polyurethanes
with different soft-segment length. J Appl Polym Sci
1996;62:6318.
[17] Kim BK, Lee SY, Xu M. Polyurethanes having shapememory effects. Polymer 1996;37:5781.
[18] Li F, Zhang X, Hou J, Xu M, Luo X, Ma D, et al. Studies
on thermally stimulated shape-memory effect of segmented
polyurethanes. J Appl Polym Sci 1997;64:15116.
ARTICLE IN PRESS
V. Sharma, P.P. Kundu / Prog. Polym. Sci. 31 (2006) 9831008
[19] Kim BK, Lee SY, Lee JS, Baek SH, Choi YJ, Xu M.
Polyurethane ionomers having shape-memory effects. Polymer 1998;39:28038.
[20] Li F, Larock RC. New soybean oilstyrenedivinylbenzene
thermosetting copolymers VI: Timetemperaturetransformation cure diagram and the effect of curing conditions on
the thermoset properties. Polym Int 2003;52:12632.
[21] Gillham JK. Formation and properties of thermosetting and
high Tg polymeric materials. Polym Eng Sci 1986;26:142933.
[22] Enns JB, Gillham JK. Timetemperaturetransformation
(TTT) cure diagram: modeling the cure behavior of
thermosets. J Appl Polym Sci 1983;28:256791.
[23] Nunez L, Taboada J, Fraga F, Nunez MR. Kinetic study
and timetemperaturetransformation cure diagram for an
epoxy-diamine system. J Appl Polym Sci 1997;66:137788.
[24] Hazer B, Demirel SI, Borcakli M, Eroglu MS, Cakmak M,
Burak E. Free radical crosslinking of unsaturated bacterial
polyesters obtained from soybean oily acids. Polym Bull
2001;46:38994.
[25] Hamurcu EE, Baysal BM. Interpenetrating polymer networks of poly (dimethylsiloxane): 1. Preparation and
characterization. Polymer 1993;34:51637.
[26] Li F, Larock RC, Marks DW, Otaigbe JU. Fish oil
thermosetting polymers: synthesis, structure, properties and
their relationships. Polymer 2000;41:792539.
[27] Gruger GH. In: Stansby ME, editor. Fish oils: their
chemistry, technology, stability, nutritional properties and
uses. Connecticut: The AVI Publishing Company; 1967.
p. 330.
[28] Li F, Larock RC, Otaigbe JU. Fish oil thermosetting
polymers: creep and recovery behavior. Polymer 2000;41:
484962.
[29] Marks DW, Li F, Pacha CM, Larock RC. Synthesis of
thermoset plastics by lewis acid initiated copolymerization of
sh oil ethyl esters and alkenes. J Appl Polym Sci
2001;81:200112.
[30] Li F, Perrenoud A, Larock RC. Thermophysical and
mechanical properties of novel polymers prepared by the
cationic copolymerization of sh oils, styrene and divinylbenzene. Polymer 2001;42:1013345.
[31] Li F, Hasjim J, Larock RC. Synthesis, structure and
thermophysical and mechanical properties of new polymers
prepared by the cationic copolymerization of corn oil,
styrene and divinylbenzene. J Appl Polym Sci 2003;90:
18308.
[32] Gunstone FD. Industrial uses of soybean oil for tomorrow,
special report1996. Ames, IA: Iowa State University and
The Iowa Soybean Promotion Board; 1995.
[33] Kinabrew RG. In Tung oil in Mississippi: the competitive
position of the industry. MS: University of Mississippi; 1952.
[34] Li F, Larock RC. Thermosetting polymers from cationic
copolymerization of tung oil: synthesis and characterization.
J Appl Polym Sci 2000;78:104456.
[35] Li F, Larock RC. Synthesis, structure and properties of
new tung oilstyrenedivinylbenzene copolymers prepared
by thermal polymerization. Biomacromolecules 2003;4:
101825.
[36] Boelhouwer C, Klassen WA, Waterman HI. Res Corresp
Suppl Res (Lond) 1954;7:S62.
[37] Rheineck AE, Austin AO. In: Myers Raymond R, Long JS,
editors. Drying oilsmodication and use: treatise on
coatings part II, vol. 1. New York: M. Dekker; 1967.
1007
ARTICLE IN PRESS
1008